Amakhonkco e-5-silicon anuka kamnandi adityaniswe ekugqibeleni

Iphupha leKhemistry leNkulungwane eliDala liyafezekiswa

Ngaphezu kwekhulu leminyaka, i-aromaticity - i-quantum mechanical phenomenon enika uzinzo olungaqhelekanga kwiimolekyuli ezithile ezimile njengeringi - yayithathwa njengeyona ndawo ikhethekileyo yekhabhoni. I-Benzene, eyafunyanwa ngo-1825 yaza yasonjululwa ngo-Agasti Kekulé ngo-1865, yaba ngumntwana weposta yeekhompawundi ezinuka kamnandi, kwaye izizukulwana zamachiza zakha amashishini apheleleyo kwisakhelo esekwe kwikhabhoni. Kodwa kwimpumelelo ebalaseleyo ephinda ibhale imithetho ye-inorganic chemistry, abaphandi baye bahlanganisa iringi yokuqala enamalungu amahlanu anevumba elipheleleyo eyenziwe ziiathom zesilicon. Le anion ye-pentasilacyclopentadienide ayimeleli nje uloyiso lokwenziwa, kodwa i-paradigm shift kwindlela esiyiqonda ngayo i-chemical bonding, ukuzinza kwe-molecular, kunye namandla angabonakaliyo e-silicon ngaphaya kwendima yayo kwi-semiconductors.

Aromaticity: Imfihlo yoZinzo eyakha iKhemistry yanamhlanje

Ukuqonda ukuba kutheni i-aromamatiki ye-silicon yonke ibalulekile, kufuneka uqale uqonde ukuba yintoni kanye kanye izisa ivumba elimnandi. Iimolekyuli ezinuka kamnandi azifani nje nesangqa-zinobume be-electron obukhethekileyo apho ii-electron ze-pi zihlanjululwa kulo lonke ulwakhiwo lwendandatho, zenza "ilifu" loxinaniso lwe-elektroni ekwabelwana ngalo elithoba kakhulu amandla e-molecule. Oku kususwa kwendawo kulandela umgaqo kaHückel, othi i-planar, i-molecule ye-cyclic ene-electrons (4n + 2) ye-pi - apho i-n iyinani elipheleleyo elingenayo i-non-negative - iya kubonisa ukuzinza okumnandi. Kwi-cyclopentadienide anion (uguqulelo lwekhabhoni), oko kuthetha ukuba ii-electron ezi-6 ekwabelwana ngazo kwii-athom zekhabhoni ezi-5.

Lo mandla uzinzo awubalulekanga. I-Benzene, iringi yekhabhoni emithandathu enevumba elimnandi, imalunga ne-150 kJ/mol izinze ngakumbi kune-hypothetical cyclohexatriene ene-double bonds yasekhaya. Olo uzinzo olongezelelekileyo yiloo nto iikhompawundi ezinuka kamnandi zilawula imichiza yezamayeza (ngaphezu kwama-85% amayeza avunyiweyo aqulathe ubuncinane iringi enye enevumba elimnandi), enze umqolo weepholima zokwenziwa, kwaye zisebenza njengabaphakathi kwiinkqubo zemichiza yemizi-mveliso exabisa amakhulu eebhiliyoni zeerandi ngonyaka.

I-cyclopentadienide anion — iringi enamalungu amahlanu ekhabhoni enuka kamnandi — isisiseko ngokulinganayo. Yenza isiseko sekhemistri yemetallocene, eyenza ukuba izinto ezincedayo ezifana neferrocene zitshintshe ichemistry ye-organometallic emva kokufunyanwa kwazo ngo-1951. Umbuzo owawukhathaza iikhemisti kangangamashumi eminyaka wawungqale: ukuba ikharbhon ingayenza le nto, kutheni ingenakho ukwenza isilicon?

Isithintelo seSilicon: Kutheni izinto ezinobunzima zixhathisa ukunuka

I-Silicon ihlala ngokuthe ngqo ngaphantsi kwekhabhoni kwitheyibhile yeperiodic, yabelana ngee-electron ezine ze-valence, kwaye yenze i-tetrahedral bonding geometries kwiikhompawundi ezininzi. Ephepheni, kufuneka ikwazi ukwenza amakhonkco amnandi. Ngokwesiko, iradiyasi enkulu yeatom yesilicon (1.17 Å xa ithelekiswa nekhabhoni 0.77 Å) kunye nokusasazwa ngakumbi kwe-3p orbitals kudala imiqobo kuhlobo olusebenzayo olusecaleni lwepi-orbital edibanayo efunwa ukuvumba.

I-silicon-silicon iibhondi eziphindwe kabini zazibhekwa njengento engenakwenzeka de iqela likaRobert West kwiYunivesithi yaseWisconsin lidibanise i-disilene yokuqala ezinzileyo ngo-1981. I-Si=Si yamandla ebhondi ephindwe kabini malunga ne-310 kJ/mol xa kuthelekiswa ne-614 kJ/mol ye-C=C. Ukuphumeza ukudityaniswa kwe-pi okwahlulwa-hlulwayo kumsesane wonke wee-athom ze-silicon ezifunekayo ukoyisa obu buthathaka bendalo ngelixa ugcina ijiyometri ecwangcisiweyo ibalulekile kungqameko lwe-orbital.

Imizamo yangaphambili ngaphezulu kwe-40+ yeminyaka ivelise i-silicon-substituted amaringi anuka kamnandi, iiheterocycles ezinesilicon, kunye noqikelelo olwahlukeneyo. Kodwa umsesane onevumba elimnandi we-homoatomic - yonke iathomu ekwisangqa ibe yisilicon - yahlala ingumnenga omhlophe wekhemistri yeqela eliphambili. Umceli mngeni wawuntlu-mbini: ukudibanisa iringi yesilicone ezintlanu ngesibalo esichanekileyo se-electron nokuyigcina izinzile ngokwaneleyo ukuba ibonakale.

Ukuphumelela: Uzinzo lobuNjineli ngoKhuseleko lweSterri

Ukuhlanganiswa okuyimpumelelo kuxhomekeke kwiqhinga eliye laba ngumgangatho wegolide wokuzinzisa iikhompawundi zeqela elisebenzayo: amaqela abambeleyo amakhulu. Ngokuqhotyoshela i-ligands enkulu, i-electron-doating ligands kwi-athomu ye-silicon nganye kwindandatho, iqela lophando liphumelele iinjongo ezintathu ezibalulekileyo ngaxeshanye. Amaqela amakhulu akhusela ngokwasemzimbeni iibhondi zesilicon-silicon ezisebenzayo kwii-reagents zangaphandle, iipropathi zabo zokunikela nge-electron zincede kuzinzisa intlawulo engalunganga yeanion, kwaye isambuku sawo esiqinileyo sinyanzelise i-close-planar geometry efunekayo kwi-pi delocalization.

Uphawu lwe-pentasilacyclopentadienide ehlanganisiweyo iqinisekise ubume bephunga ngeendlela ezininzi ezizimeleyo:

• X-ray crystallography iveze ubude obusondele obulinganayo bebhondi yeSi-Si ejikeleze iringi (~ 2.25 Å), ihambelana nokudityaniswa kwebhondi endaweni yokutshintshana kweebhondi ezingatshatanga neziphindwe kabini
• I-Nuclear magnetic resonance (NMR) spectroscopy ibonise iipateni ze-deshielding ehambelana nendandatho enevumba elimnandi
• Izibalo ze-Nucleus-independent chemical shift (NICS)zivelise ixabiso elibi kakhulu kwiziko le-ring, isalathisi esamkelwe ngokubanzi se-aromatics
• I-UV-ebonakalayo i-spectroscopy ebonisiweyo iimpawu zokufunxa ezihambelana neenguqu ze-pi-electron ezisusiweyo kwisakhelo se-silicon
• Izibalo ze-Density functional theory (DFT) ziqinisekise amandla amakhulu okuzinzisa okunuka kamnandi, kuqikelelwa kwi-50-70 kJ/mol

Ngelixa amandla okuzinzisa anuka kamnandi esezantsi kune-benzene's 150 kJ/mol, makhulu ngokwaneleyo ukwenza ikhompawundi ibe yodwa kwaye ibonakale kwiqondo lobushushu begumbi phantsi kweemeko zemo ye-inert-impumelelo engummangaliso yemolekyuli uninzi lweekhemisti ezikholelwa ukuba ayinakubakho ngendlela ezinzileyo.

Ngaphaya kweBhentshi yeLebhu: Iimpembelelo zeLizwe lokwenyani

Ukwenziwa kweeringi zesilicon enuka kamnandi kuvula iipaseji zophando ezidlulela ngaphaya kokufuna ukwazi. Iikhompawundi ezinuka kamnandi ezisekwe kwi-silicon zinokubonisa iimpawu ze-elektroniki ezahluke kakhulu kwi-carbon analogs zazo, kunye nosetyenziso olunokubakho oluthatha amashishini akwixabiso eliphezulu.

Ukufunyanwa kwe-aromatics ye-silicon yonke akongezi nje i-compound entsha kwikhathalogu - kuseka iklasi entsha ngokupheleleyo ye-molecular architecture. Zonke izicelo ezakhelwe kwi-carbon aromatics kwiminyaka eyi-160 edlulileyo ngoku zine-silicon-based counterpart elinde ukuphononongwa, nganye inezinto ezinokuthi zenzeke nge-elektroniki, i-optical, kunye ne-catalytic.

Kwiteknoloji ye-semiconductor, apho isilicon sele ilawula njengesiseko, iikhompawundi zesilicon ezinuka kamnandi zinokusebenza njengezixhobo ze-elektroniki zesikali semolekyuli. Ii-elektroni ze-pi eziye zasuswa kula makhonkco zinokuthi ziqhube intlawulo ngeendlela ezahlukileyo kwi-silicon yesambuku, ebonelela ngeendlela eziya kwi-electronics molekyuli kunye ne-quantum computing substrates. Ngemarike ye-semiconductor yehlabathi kuqikelelwa ukuba iya kudlula i-1 yetriliyoni yeedola ngo-2030, nkqu nenkqubela phambili eyongezelelweyo kwi-silicon-based molecular electronics ineempembelelo ezinkulu zorhwebo.

Kwi-photovoltaics, iiringi ezinevumba elimnandi zesilicon zinokusebenza njengenoveli yokuvuna ukukhanya kwechromophores. Iipropati zabo zokufunxa kunye nokukhupha - ziyakwazi ukuguqulwa ngokuguqulwa kwendawo - zinokwenza iiklasi ezintsha ze-silicon-based organic light-emitting diode (OLEDs) okanye izinzwa zeseli zelanga ezivala umsantsa phakathi kwe-silicon photovoltaics kunye nobuchwepheshe obuvelayo belanga belanga.

Umbuzo we-Catalyst: I-Silicon Metallocenes kwi-Horizon

Mhlawumbi elona themba linika umdla ngokukhawuleza lithuba le-silicon-based metallocenes. ICarbon's cyclopentadienide anion yenza iikhompawundi zesandwich phantse zonke iinguqu zesinyithi, kwaye ezi metallocenes zizixhobo eziyimfuneko kwikhemistri yepolymer. I-Ziegler-Natta kunye ne-metallocene catalysts kunye zixhasa ukuveliswa kweetoni ezingaphezu kwe-100 lezigidi ze-polyethylene kunye ne-polypropylene ngonyaka - imarike exabisa malunga nama-200 eebhiliyoni zeedola.

Ukuba i-pentasilacyclopentadienide inokulungelelaniswa kwinguqu yesinyithi ngendlela ye-carbon analog yayo eyenza ngayo, i-silicon metallocenes enesiphumo iya kuba neempawu ezisisiseko ezahlukileyo kunye ne-elektroniki. Umsesane omkhulu wesilicon unokudala "i-angle yokuluma" ebanzi ngeenxa zonke kumbindi wentsimbi, enokwenza ukuba kukhethwe okutsha kwi-olefin polymerization, ukusebenza kwe-CH, kunye nolunye utshintsho oluyimpembelelo. Nditsho nophuculo olungephi ekusebenzeni kakuhle kolu shishino luguqulela kwiibhiliyoni zeedola ngexabiso kunye nokuncipha okubonakalayo kokusetyenziswa kwamandla kunye nenkcitho.

Uphononongo lwakwangoko lokubala lubonisa ukuba i-silicon metallocenes ingaphinda ibonise iipropati eziphuculweyo zemagneti xa kuthelekiswa nekhabhoni ehambelana nayo, ukuvulwa kwezicelo kwi-spintronics kunye nezixhobo zokugcina idatha yamagnetic. Intsimi iselula, kodwa isiseko sethiyori sele sibekiwe kumaqela amaninzi ophando kwihlabathi jikelele.

Ukulawula Ukuntsonkotha kweMisebenzi yoPhando lwangoku

Ukuphumelela okufana neringi yesilicon enuka kamnandi ngumzekelo wokuntsokotha kophando lwezenzululwazi lwala maxesha - iiprojekthi zeminyaka emininzi ezibandakanya amaqela ahlukeneyo, izixhobo ezixabisa kakhulu, ukuthotyelwa kwemithetho, ulawulo lwezibonelelo, kunye nentsebenziswano ekhulayo yehlabathi. Amaqela ophando kunye nabaqalayo abathengisa izinto abazifumeneyo bajongana nemingeni yokusebenza ekhuphisana nabo naliphi na ishishini eliphakathi: ukulandelela iiprojekthi ezininzi ezisebenzayo, ukulawula ukuthengwa kunye nobudlelwane bomthengisi kwiikhemikhali ezikhethekileyo kunye nezixhobo, ukuphatha i-HR kumaqela ajikelezayo e-postdocs kunye nabafundi abaphumeleleyo, kunye nokugcina iirekhodi ezicokisekileyo zokukhusela ipropathi yengqondo.

Amaqonga afana ne-Mewayz ajongana ngqo nobu bunzima bokusebenza. Ngeemodyuli ezidibeneyo ze-207 ezithatha i-CRM, i-invoyisi, ulawulo lweprojekthi, i-HR, kunye nohlalutyo, i-Mewayz inika imibutho eqhutywe ngophando inkqubo enye yokulawula icala loshishino lokutsha. Kunokuba zidibanise iispredishithi, amakhonkco e-imeyile, kunye nezixhobo zesoftware eziyekiweyo, amaqela anokulandelela imida yeprojekthi, alawule ii-invoyisi zababoneleli kwii-reagents zaselabhoratri, ukulungelelanisa iishedyuli zeqela, kunye nokuvelisa iingxelo zemali ezifunwa zii-arhente zenkxaso - zonke zisuka kwiqonga elinye. Kumaqela angama-138,000+ asele esebenzisa i-Mewayz kwihlabathi jikelele, olu hlobo lolawulo lokusebenza olusembindini luthetha ixesha elincinci kulawulo oluphezulu kunye nexesha elingakumbi lokutyhala imida yento enokufikelela kwisayensi.

Yintoni ezayo ngokulandelayo: Itheyibhile yePeriodic ineeMfihlo ezingakumbi

Ukudityaniswa okuyimpumelelo kweringi ye-silicon enevumba elimnandi ngokukhawuleza kuphakamisa umbuzo: uthini ngezinye izinto zeQela le-14? I-Germanium, i-tin, kunye nokukhokela zonke ukwabelana nge-silicon's four-valence-electron configuration, kwaye nganye inikezela ngeseti yayo yemingeni ekuphumezeni iinkqubo zeringi ezizinzileyo. Iringi ze-Germanium ezinevumba elimnandi, ngokukodwa, ngoku zijongwa njengeyona nto ibonakalayo ekujoliswe kuyo kwixesha elikufuphi, ngokunikwa indawo ephakathi yegermanium phakathi kwesilicon kunye nezinto ezinzima.

Ngaphaya kweQela le-14, ingqikelelo yokuvumba sele yandisiwe ukuya kumaqela e-boron (i-boranes kunye ne-carboranes zibonisa ukuvumba kwe-three-dimensional), amakhonkco e-phosphorus, kunye neenkqubo ezinuka kamnandi zentsimbi ezifana ne-Al4²⁻ tetraanion yokuqala ephawulwe ngo-2001. iibhloko ezinezakhiwo ezingenako ukuphinda-phinda ziinkqubo ezisekwe kwikhabhoni iyodwa.

I-synthesis ye-pentasilacyclopentadienide iphinda iqinisekise intsingiselo ebanzi kwi-chemistry yanamhlanje: ukuhlolwa okucwangcisiweyo kwezinto eziphambili zeqela le-bonding motifs ngaphambili ebegcinelwe i-carbon. Kule minyaka ingamashumi amabini idlulileyo, iikhompawundi ezizinzileyo eziqulathe iibhondi ezintathu ze-silicon-silicon, i-phosphorus-phosphorus triple bond, kunye ne-boron-boron triple bond zonke ziye zafezekiswa. Nganye kwezi zinto zafunyaniswayo zandulelwa ngamashumi eminyaka yemizamo engaphumeleliyo kunye nokuthandabuza kwethiyori, kwaye nganye ivule iindlela ezintsha zoyilo lwemathiriyeli.

Into eyenza iringi yesilicon enuka kamnandi ibaluleke ngakumbi kuqhagamshelo lwayo oluthe ngqo kwenye yeengqikelelo ezibaluleke kakhulu kurhwebo lwekhemistri. I-aromaticity ayiyonto yokuthatha izifundo - yipropathi yemolekyuli exhasa amayeza, iiplastiki, idayi, iziqhushumbisi, iikhemikhali zezolimo kunye nezixhobo zombane. Ukwandisa le propati kwi-silicon akugqibezeli nje umqolo kwitafile yencwadi. Isungula ixesha elitsha le-silicon chemistry apho isakhono sesiqalelo sinabela ngaphaya kweecrystalline wafers kwiichips zethu zekhompyuter kunye nakwindawo yoyilo lwemolekyuli, kude kube ngoku, ibiyeyekhabhoni kuphela.

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Imibuzo Ebuzwa Rhoqo

Yintoni iringi yesilicon enuka kamnandi?

Iringi yesilicon enuka kamnandi yiathom apho iiathom zesilicon zenza ulwakhiwo oluzinzileyo, olumile okwesangqa olunozinzo olukhethekileyo "olunukayo", ipropathi ekudala kucingelwa ukuba iphelele kwikhabhoni kuphela. Oku kubandakanya ii-electron ekwabelwana ngazo ngokulinganayo kwiringi, nto leyo eyenza ukuba yomelele ngokungaqhelekanga. Oku kufunyenweyo kwandisa ingqikelelo yevumba elimnandi ngaphaya kwekhemistri ephilayo ukuya kummandla wezinto ezingaphiliyo ezifana nesilicon.

Kutheni oku kudityaniswa kujongwa njengempumelelo ebalulekileyo?

Ngaphaya kwenkulungwane, ukuvumba kwevumba ibiluphawu oluchazayo lwe-carbon-based molekyuli njenge benzene. Ukudala ngokuyimpumelelo iringi ezinzileyo, enevumba elimnandi ngokupheleleyo kwisilicon ingqina ukuba le ngcamango yekhemikhali isisiseko ayingqalanga nekhabhoni. Iphinda ibhale ulwazi lweencwadi zesikhokelo kwaye ivule amathuba amatsha amakhulu okuyila imathiriyeli entsha eneempawu ezizodwa zombane ebezingenakucingelwa ngaphambili kwiikhompawundi zesilicon.

Zintoni ezinokuthi zibe kho usetyenziso lwala makhonkco esilicon?

Ngelixa sisekwizigaba zophando lwakwangoko, la makhonkco e-silicon anevumba elimnandi angakhokelela kutshintsho lwezicelo. Ulwakhiwo lwabo olulodwa lwe-elektroniki lunokubotshelelwa ukwenza iintlobo ezintsha zee-semiconductors, imathiriyeli ephucukileyo ye-elektroniki, okanye ii-catalysts ezisebenza ngakumbi. Ukuqonda indlela yokulawula ukuvumba kwe-silicon kunokuvula amasebe amatsha ngokupheleleyo enzululwazi yemathiriyeli, indawo ephambili yokufunda kwiikhemisti zisebenzisa izixhobo ezifana neMewayz (eneemodyuli ezingama-207 kwi-19 yeedola / mo).

Ngaba oku kufunyanisiweyo kunxulumana njani ne-silicon chemistry ekhoyo?

Oku kufunyaniswe kucela umngeni kwimbono yemveli ye-silicon chemistry. Ngokuqhelekileyo, i-silicon yenza iibhondi enye, idala amatyathanga kunye nezakhiwo ezifana ne-alkanes (i-hydrocarbons egcweleyo). Ukwenziwa kwesangqa esinevumba elizinzileyo kubonisa ukuba i-silicon inokuthatha inxaxheba kwiinkqubo zokudibanisa eziyinkimbinkimbi, ezifana nekhabhoni, ezinokukhokelela kwiklasi entsha ye-silicon-based compounds kunye neempawu ezahlukileyo kwii-silicones eziqhelekileyo kunye ne-silanes.

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